Halocarboxylic acid anilides

ABSTRACT

IN WHICH X1 AND X2 STAND FOR CHLORINE, FLUORINE OR BROMINE, X3 REPRESENTS HYDROGEN, CHLORINE, FLUORINE, BROMINE OR CHL2, Z MEANS NO2 OR CF3, HAL REPRESENTS IDENTICAL OR DIFFERENT HALOGEN ATOMS, PREFERABLY CHLORINE, BROMINE OR FLUORINE, N1 BEING ZERO OR 1 OR 2, AND THE SUM OF ZERO OR 1 OR 2, N3 BEING ZERO OR 1 OR 2 OR 3, N2 BEING N1 + N2 + N3 IS AN INTEGER IN THE RANGE OF FROM 1 TO 4. THE NOVEL COMPOUNDS HAVE A GOOD HERBICIDAL EFFECT AGAINST A SERIES OF MONO- AND DICOTYLEDONS.   (X1-C(-X2)(-X3)-CO-NH-),(HAL-)N1,(NC-)N2,(F3C-)N2,Z-BENZENE   THE INVENTION PROVIDES SUBSTITUTED HALOCARBOXYLIC ACID ANILIDES OF THE GENERAL FORMULA A

United States Patent Ofl'ice 3,794,683 Patented Feb. 26, 1974 3,794,683 HALOCARBOXYLIC ACID ANILIDES Gustav Gassner, Kelkheim, Taunus, Gerhard Horlein, Frankfurt am Main, and Hans Rochling, Altenhain, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing. Filed Aug. 24, 1971, Ser. No. 174,564 Claims priority, application Germany, Aug. 26, 1970, P 20 42 300.1 Int. Cl. C07c 103/32 US. Cl. 260-562 B 4 Claims ABSTRACT OF THE DISCLOSURE The invention provides substituted halocarboxylic acid anilides of the general formula A in which X and X stand for chlorine, fluorine or bromine, X represents hydrogen, chlorine, fluorine, bromine or CHCl Z means N or CF Hal represents identical or different halogen atoms, preferably chlorine, bromine or fluorine, n being zero or 1 or 2 or 3, n being zero or 1 or 2, n, being zero or 1 or 2, and the sum of n |n +n is an integer in the range of from 1 to 4. The novel compounds have a good herbicidal effect against a series of monoand dicotyledons.

The present invention relates to substituted halocarboxylic acid anilides of the general formula A in which X and X stand for chlorine, fluorine or bromine, X represents hydrogen, chlorine, fluorine, bromine or CHCl Z means N0 or CF Hal represents identical or different halogen atoms, preferably chlorine, bromine or fluorine, n; being Zero or 1 or 2 or 3, n being zero or 1 or 2, n being zero or 1 or 2, and the sum of n +n +n is an integer in the range of from 1 to 4.

The present invention also relates to a process for the preparation of halocarboxylic acid anilides of the general Formula A which comprises reacting in known manner, preferably in an inert solvent, correspondingly substituted anilines (a) with the corresponding halocarboxylic acid halides in the presence of a tertiary base or (b) with the corresponding halocarboxylic anhydrides in the presence of concentrated sulfuric acid or the respective halocarboxylic acid. If desired, the product obtained may be nitrated with potassium nitrate or nitric acid in sulfuric acid.

From among the compounds of the invention there are preferred those which carry a nitro group at the phenyl nucleus besides further substituents of the above definition, and a trifluoromethyl, trichloromethyl, or dichlorodifluoroethyl group in the acid radical, i.e. compounds in which the radical of the general Formula A stands for CCl 0B,, or

OF OHCl The anilines used as starting material can be prepared by known methods described in literature.

Suitable anilines are, for example: 2,5-di-(trifluoromethyl)-4-nitroaniline 3,5-di-(trifluoromethyl)-2-nitroaniline 3,5-ditrifluoromethyl) -aniline 3 ,S-di- (trifiuoromehtyl -4-nitroaniline 2,6-dichloro-4-nitroaniline Z-fluoro-5-chloro-4-nitroaniline 2,4,-6-trichloro-3-nitroaniline 3,4,S-trichloro-2-nitroaniline 2,3,6-trichloro-4-nitroaniline 3,4,6-trichloro-aniline 3,4,-6-trichloro-2-nitroaniline 2,3,6-trifiuoro-4-nitroaniline 2,3,6-triflu0ro-3-nitroaniline 2,4,6-tribromo-3-nitroaniline 4-cyano-2-nitroaniline 2-cyano-4-nitroaniline 2,4-dicyano-S-triflitoromethylaniline 2,6-dichloro-4-trifluoromethylaniline 2,3,6-trichloro-5-trifiuoromethylaniline 2,6-dichloroaniline 3,4,5-trichloroaniline 2,4,6-trichloroaniline 2,4,5-trifluoroaniline 3,5-dicyanoaniline When the last mentioned anilines, which do not contain a nitro group are used, the acylated aniline may subsequently be nitrated.

As halocarboxylic acid halides, preferably halocarboxylic acid chlorides or fluorides, or halocarboxylic anhydrides there are used, for example, compounds in which the radical C-Xz stands for CF CCl CBr CCIF CClBr CHCI CHBl'g, CHF CF CHCl CFCl or CFBr preferably CF CCl or CF CHCl- The compounds of the general Formula A can be prepared in inert solvents, for example benzene, toluene, xylene, chloro-benzene, petroleum ether boiling at about -110 C., or carbon tetrachloride, in the presence of an about molar amount of a tertiary base, for example pyridine or triethylamine, by adding the corresponding halocarboxylic acid halide in an approximately molar amount, calculated on the aniline used. During the addition of the acid halide, the reaction mixture warms up so that cooling may be advantageous. In general, the reaction is carried out at a temperature in the range of from 20 to 0., preferably 40 to 80 C. After addition of the acid halide, the reaction mixture is stirred for a further 3 to 5 hours at 80l10 C.

Alternatively, the compounds of the invention can be prepared in the aforesaid inert solvents in the presence of catalytic amounts of concentrated sulfuric acid or the corresponding halocarboxylic acid, for example in an amount of 0.01 to 0.1 mole per mole of aniline used, by reacting the aniline with the corresponding halocarboxylic anhydrides. In this case, the reaction temperature should be in the range of from 80 to C., preferably 110 to 140 C.

A further object of the present invention are herbicides characterized by a content of halocarboxylic acid anilides of the general Formula A.

It is known that anilides may have herbicidal properties. Propanil (3,4-dichloro-propion-anilide), (German Pat. No. 1,039,779, British Pat. No. 903,766), for example, is a commercially available herbicide. It was used in the following examples as comparative agent.

It has been found that the compounds of the invention exhibit an efiect as pre-emergence herbicides that is surprising for the class of anilides and, for example, which is superior to that of propanil.

The compounds of the invention are especially efi'ective, however, as post-emergence herbicides. In this case, too, the novel compounds are distinctly superior to propanil and dinoseb-acetate. A detailed description of the biological action of the compounds of the invention follows below.

The compounds of the invention can be used as herbicides in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting powders or granules.

Wettable powders are preparations that can be uniformly dispersed in water and contain, besides an inert substance, a wetting agent, for example polyoxethylated alkylphenols, polyoxethylated oleylor stearylamines, alkylor alkylphenyl sulfonates and dispersing agents, for example the sodium salt of lignin-sulfonic acid, of 2,2- dinaphthyhnethane-6,6'-disulfonic acid, of dibutyl-naphthalene-sulfonic acid or sodium oleylmethyltauride.

Suitable grinding auxiliaries are inorganic or organic salts such as sodium sulfate, ammonium sulfate, sodium carbonate, sodium bicarbonate, sodium thiosulfate, sodium stearate or sodium acetate.

Emulsion concentrates are obtained by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or aromatic hydrocarbons having a higher boiling point. To obtain suspensions or emulsions in water having good properties, wetting agents as specified above are also added.

Dusting powders are obtained by grinding the active ingredients with finely divided, solid substances, for example talc, natural clays, pyrophillite or diatomaceous earths.

Spraying solutions commercially available as aerosol sprays contain the active ingredient dissolved in an organic solvent, and in addition thereto a propellant, for example a mixture of fluorohydrocarbons.

Granules can be produced by atomizing the active ingredient on to an absorptive, granulated inert material, or by applying concentrates of the active ingredient to the surface of a support, for example sand, kaolinite or a granulated inert material with the aid of an adhesive, for example polyvinyl alcohol, the sodium salt of polyacrylic acid, or mineral oils. Alternatively, suitable active ingredients may be made into granules, if desired in admixture with fertilizers, in the manner commonly used for the manufacture of granulated fertilizers.

The commercial herbicidal preparations contain varying concentrations of the active ingredients. In wettable powders the concentration of active ingredients varies, for example, from about 10 to 95%, the remainder being the above formulation additives. Emulsion concentrates contain about 10 to 80% of active ingredient, while dusting powders mostly contain 5 to 20% of active ingredient and sprayable solutions about 2 to 20%.

In the case of granules, the content of active ingredient partially depends on whether the active ingredient is liquid or solid and on the type of granulation auxiliary or filler used.

For application, the wettable powder or emulsifiable concentrate is diluted in usual manner with water. Dusts and granulated formulations as well as sprayable solutions are not diluted further with an inert substance before their application. The amount applied varies with the external conditions, such as temperature, humidity and the like. In general, about 0.015 to 0.25 gram and preferably about 0.03 to 0.12 gram of active ingredient per square meter are used.

The herbicides according to the present invention may be combined with other herbicides and soil insecticides. Known herbicides which may be combined with the novel compounds of the invention are, for example:

Urea derivatives: linuron, chloroxuron, monolinuron,

fluometuron, diuron Triazine derivatives: simazin, atrazin, ametryne, prometryne, desmetryne, methoprotryne;

Urazil derivatives: lenacil, bromacil;

Pyrazone derivating: 1-phenyl-4-arnino-5-chloropyridazone (6);

Growth-promoting preparations: 2,4-dichlorophenoxyacetic acid, 4-chloroZ-methylphenoxy-acetic acid, 2,4,5- trichlorophenoxyacetic acid, 4-chloro-2-methylphenoxy-butyric acid, 2,3,6-trichloro-benzoic acid;

Carbamic acid derivatives: barban, phenmediphan, triallate, diallate, vernolate and 2-chloroallyl-N,N-diethyldithiocarbamate, swep;

Dinitrophenol derivatives: dinitro-orthocresol, dinoseb,

dinosebacetate;

Chlorinated aliphatic acids: trichloroacetic acid, dalapon;

Amides: diphenamide, N,N-diallyl-chloroacetamide;

Dipyridilium compounds: paraquat, biquat, morfamquat;

Anilides: N-(3,4-dichlorophenyl)-methacrylamide, propanil, solan, monalide, 2-chloro-2',6-diethyl-N-(methoxymethyl)-acetanilide, propachlor;

Nitriles: dichlorbenil, ioxynil;

Other preparations: flurenol, 3,4-dichloropropionanilide,

bensulide, monosodium methyl arsonate, 4-triflu0romethyl-2,4'-dinitr-odiphenyl ether.

When the active ingredients according to the invention are mixed with fertilizers, preparations are obtained which simultaneously have a fertilizing and a herbicidal eifect.

A wettable powder which is readily dispersible in water can be obtained by mixing 25 parts by weight of an active ingredient according to the invention,

64 parts by weight of kaolin-containing quartz as inert substance,

10 parts by weight of the potassium salt of lignin-sulfonic acid,

1 part by weight of sodium oleylmethyl tauride as wetting and dispersing agent, and grinding the mixture obtained in a disk attrition mill.

A dusting powder having good herbicidal properties can be obtained by mixing 10 parts by weight of an active ingredient according to the invention and parts by weight of talcum as inert substance,

and grinding the mixture obtained in a cross-beater mill. An emulsifiable concentrate consists, for example, of

15 parts by weight of an active ingredient according to the invention 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of nonyl(ethoxyl) phenol as emulsifier.

The following examples illustrate the invention. The acylation of the aniline derivatives may be carried out either with a halocarboxylic acid chloride in the presence of a tertiary base with a halocarboxylic anhydride or in the presence of concentrated sulfuric acid or the corresponding halocarboxylic acid. Alternatively, an acylated aniline may be subsequently nitrated.

dichloro -propionanilide CF3- -NHCO-CF2CHCI2 N O 1 C F a 877 grams (3.2 moles) of 2-nitro-5-amino-hexafluorop-xylene (prepared by first chlorinating, then fluorinating and nitrating 2-chloro-p-xylene in the side chain and finally exchanging the ring chlorine atom for the amino group) were dissolved in 6.4 liters if dried toluene and 467 mil-liliters (3.36 moles) of triethyl amine were added. The mixture was heated at 80 C., the heating bath was removed when the indicated temperature had been reached and 664 grams (3.36 moles) of OL,0L-dl.flll0l'OB,B-dlh10- ro-propionic acid chloride (obtained as described by G. Troilo and G. Gambaretto, Ann. Chim. 58 (1968), No. 1 pp. 25-31) were added dropwise. The reaction mixture was heated for 4 hours at 100 C., after cooling the formed hydrochloride was separated by filtration, the filtrate was concentrated and the residue was distilled without column under highly reduced pressure. Yield 1170 grams'(84%) boiling point under 0.1 mm. Hg 136-140 C.

After distillation, the substance became solid and was recrystallized from n-hexane. It had a melting point of 49-50 C.

AnalysisFC H Cl F N O Cal.: C, 0.92% H, 6.44% N. Found: 31.0% C, 0.9% H, 6.4% N.

EXAMPLE 2 2,5-di-(trifluoromethyl)-4-nitro-trifluoroacetanilide C F3 NH-CO-C Fa NO CF;

27.4 grams (0.1 mole) of 2-nitro-5-amino-hexafiuorop-xylene in 200 milliliters of dried toluene were mixed with 2 milliliters of trifluoroacetic acid and, while stirring, 3

15.4 milliliters (0.11 mole) of trifluoroacetic anhydride were dropped in. The reaction mixture was refluxed for 4 hours, then concentrated and the residue was crystallized from petroleum ether boiling at 80-110 C.

Yield 22.3 grams melting point 71-73 C. Analysis.-C H F N O (370): Cal.: 32.4% C, 0.81% H, 7.56% N. Found: 32.8% C, 1.0% H, 7.2% N.

EXAMPLE 3 2-nitro-3,4,5-trichloro-(u,a-difluoro- 3,fl-dichloro) propionanilide Cl NH-CO-C F -CHClg 482.0 grams (1.35 moles) of 3,4,5-t1iCh101O-(oc,a-difluoro-fi,;9-dich1oro)-propionanilide (prepared as described in Example 1) was introduced into 14,000 milliliters of concentrated sulfuric acid and, over a period of 6 hours, 136.1 grams (1.35 moles) of potassium nitrate were added in portions, whereby the temperature in the reaction vessel rose to 32 C. The reaction mixture was stirred for 9 hours and then allowed to stand for 24 hours at room temperature. Subsequently, the reaction mixture was stirred into a mixture of ice and water, the solid matter was separated by suction filtration, washed with water until neutral and dried.

Yield 500 grams (92%) melting point 96-98 C.

Analysis.C H Cl F N O (402.5): Cal.: 26.8% C, 0.75% H, 6.96% N. Found: 27.3% C, 0.6% H, 6.7% N.

In the following Table I compounds are listed which were prepared in a manner analogous to that described in Examples 1, 2, and 3.

TABLE I Examples 4-26 Mode of Expreparation ample according to Yield Melting Empirical formula (molecular weight) No. Chemical designation Exemplepercent point, 0. analysis values in percent 4 2,5-di-tritiuoromethyl-4-nitro-trichloroaeetanilide (IV) 2 73 0.5 CloHaClsFdNiOx (419.5)

136-139 Cal'd: 28.62 C, 0.71 H, 6.68 N

Found: 28.4 C, 0.8 H, 6.8 N

5 2,5-di-trifluoromethyl-4-nitro-dibromoaeetanilide (V) 2 131-133 C10H(B!'2F6N203 (473.8)

Cal'd: 25.4 C, 0.84 H, 5.92 N Found: 25.1 C, 0.91 H, 6.01 N

6 2-nitro-3,4,5-trlehlorotrifiuoroacetanilide (VI) 2and3 70 142-143 CsHzClgFaNaOa (337.5)

- Cal'd: 28.5 C, 0.59 H, 8.31 N

Found: 28.8 G, 0.3 H, 3.6 N

7 2-nitro-3,4,5-trichlorotriehloro-acetanilide (VII) 2and3 82 112 C HzCltNaO; (387) Cald: 24.8 C, 0.52 H, 7.24 N

Found: 25.2 C, 0.8 H, 7.2 N

8 2-nitro-3,4,6-trichlorotrifluoroacetanilide (VIII) 2 and 3 69 127-128 CsHzClaFsNzOa (337.5)

' Cal'd: 28.5 C, 0.59 H, 8.31 N

Found: 28.6 C, 0.7 H, 8.0 N

9 2-nitr0-3,4,6-trichlorotriehloro-acetanilide (IX) 2 and?! 89 cgHzcloNzos (387) Cald: 24.8 C, 0.52 H, 7.24 N

' Found: 24.8 C, 0.8 H, 7 3 N 10 2-cyano-4-nitro-(a,a-difluoro-fl,fi-dichloro)-propionanilide (X) 1 93 -131 C1oH ClzFzN3O (324.0)

Cal'd: 37.0 C, 1.54 H, 12.95 N Found: 37.5 C, 1.6 H, 13.1 N

11 2-cyano-4-nitro-trifluoroacetanilide (XI) 2 62 122-124 ooHtNaosFs (259) Cal'd: 41.7 C, 1.54 H, 16.2 N Found: 41.7 C, 1.5 H, 16.1 N

12.. 2-cyauo-4-nitro-trlchloroacetanillde (XII) 2 54 128-130 CnHtClaNgOz (308.5) Cal'd: 35.0 C, 1.29 H, 13.6 N Found: 35.2 G, 1.2 H 13.7 N

See footnote at end of table.

TABLE I-Continued Mode of Ex preparation ample according to Yield Melting Empirical formula (molecular weight) No. Chemical designation Example percent point, 0. analysis values in percent 13"--- 2-flnoro-4-nitro-5-chloro-(a,a-difluoro- 5,fl-dichloro)-propion- 1 and 3 63 87-88 CaHrClsFsNzOa amlldo 1 (XIII). Cal'd: 30.7 C, 1.13 H, 8.0 N Found: 30.4 C, 1.2 H, 8.1 N

14 2-fluoro-4nitro-5-chlorotriflu0roacetanilide (XIV) 2 and3 50 89 C5H3C1F4N203 (286.5) Cal'd: 33.48 C, 1.05 H, 9.78 N Found: 83.8 C, 1.1 H, 9.7 N

2-fluoro-4-nitro-5-chlorotrichloroacetanilide (XV) 2 and3 50 cgHgchFNzoa (336.0)

Cald: 28.6 o, 0.89 H, 8.34 N Found: 28.45 C, 0.87 H, 8.39 N

16 2-m'tro-3,5-di-trifluoromethyl-(a,a-diflu0r0-fl,B-dich1oro)- 62 66-68 OllHlClgFgNOa (435) propionanilide (XVI). Cal'd: 30.3 C, 0.92 H, 6.45 N

Found: 30.6 C, 1.5 H, 6.8 N

17 2-nitro-3,5-di-trifluorotrifluoroacetanilide (XVIII) 2 81 142-144 CiuHaFoNzOa (370) Cald: 32.45 C, 0.81 H, 7.56 N

Found: 32.2 C, 1.3 H, 7.4 N

18....- 2-nitro-3,5-di-trifluoromethyl-trichloroacetanilide (XVIII)...:..-; 63 64-66 CiuHgClsFeNqO: (419.5)

Cal'd: 28.6 C 0.71 H, 6.68 N Found: 28.4 o, 0.9 H, 6.7 N

19....'. 2,3,(i-trichloro-5-trifluoromethyl-trichloroacetanilide (XIX)-.;.';..- 63 119120 CQHjClGNflO (410) Cal'd: 26.3 C, 0.48 H, 3.4 N, 52.0 01 Found: 26.4 C, 0.5 H, 3.3 N, 52.4 01

20-. 2,4,6-trichloro-3-nitrotrichloroacetanilide (XX) 2 and 3 139-140 oamoumoa (387) CaLd: 24.8 C, 0.52 H, 7.24 N Found: 24.7 C, 0.7 H, 7.2 N

21. 2,4 S-trichloro-B-nitro-(a,a-difluoro-fi,fl-dichloro)-propionanillde 1 and 2 89 140-141 CoHaClsFzNzO; (402.5)

XXI Cald: 26.8 c, 0.75 H, 6.96 N

Found: 27.2 C, 0.9 H, 7.0 N

22".-- 2,3,6-tricl1loro-4-nitrotrichloroacetanillde (XXII) 64 130-131 CaHiCltNqO; (387) Cald: 24.8 C 0.52 H, 7.27 N Found: 25.2 o, 0.6 H, 7.2 N

23 2- t o-4-c ano- -difluoro -dichloro)- r0 ionanilide 61 72-74 C10H5C1QF2N3O3 (324) iir xnri. (M p B p p Cald: 37.0 c, 1.54 H, 12.95 N

Found: 37.5 C, 1.6 H, 13.3 N

24..." 2,4,6-t1'ibromo-3-nitro-(a,a-difiuoro-fl,-fl-dichloro)-propionanilide 11. 3 177 CnHzBIgClaFzNzOg (534.7)

(XXIV). Cald: 20.2 o, 0.37 H, 5.23 N

Found: 21.1 C, 0.6 H, 5.4 N

2- -3 4 -t i hloro- -difluoro- -dichlo1'o ro ionanilide 1 and 3..::.; 75 110 00H 01 FlNflo (402.5) 25 23% r c p p Cal'd: 26.8 o, 0.75 H 6.06 N Found: 27.4 o, 0.8 n, 7.3 N

26.... 3,5-di-(trlfluoromethyl)-4'nitro-(a,a-difluoro-,5-dich1oro- 126-127 C11H|Cl1FaN|O3 (435.0)

' 1i XXVI Cald: 30.3 C 0.92 H, 6.44 N pmplmam Found: 30.3 o, 1.0 H 5.9 N

1 Preparation of aniline: G. 0. Finger, F. W. Kruse, .T.A.C.S., 78, 0034 (1956); G. C. Finger, et al., J.A.C.S., 81, 94-101 (1959).

EXAMPLE 27 Seeds of different types of weeds and crop plants were sown in pots filled with loamy soil and covered with a layer of soil about 1 cm. thick. On the day of sowing the surface of the soil was sprayed with suspension of wettable powders containing as active ingredient Compounds I or X, respectively (cf. Examples 1 and 10). The wettable powders had the composition specified in the paragraph preceding the examples.

This method is called pre-emergence process. The amount of liquid applied was 800 liters, calculated on 1 hectare. The pots were placed in a greenhouse and the result was evaluated after 4 weeks.

In the following tables the damage is indicated in percent, 100 corresponding to complete killing and 0 to no damage at all. The remark damage in some of the tables indicates that the respective active ingredient caused severe damage of the treated crop plants so that an application of this herbicide cannot be considered successful in the respective crop.

As comparative compound, the chemically closely related 3,4-dichloropropionanilide (propanil) known in practice was used, which is well tolerated by many crop plants.

Stellaria media 25 100 Amaramhus retroflezu 45 100 Eleusine indica 0 95 Leptochloa dubia 0 95 Crop plants:

Gossupium hirsutum (cotton). 0 0 0 Helianthus annuus (sunflower O 10 Lycopersicum escule'ntum (tomato t) 0 10 10 Brassica oleracea (cabbage plant) 0 0 10 .Pisum sativum (pea). 0 0

Vicia faba (horse bean) 0 10 Arachzs hypogcea (peanut) 0 0 Nocotiana tabacum (tobacco plant) 0 0 Apium graveolem (celery pant) 0 0 TABLE A Effect against weeds and crop plants in the pre-emergence process with 0.12 g. of active ingredient per square meter of soil surface Compound 5 Pro- Type of plant; panil I X Weeds:

Sinapia arvemis 30 100 Ipo'moea purp'ureau 0 Echinochloa crux-gal 7 0 60 7 P02 0 Anthemis arvensis Damage.

The table shows that in a concentration of 0.12 gram 75 of active ingredient per square meter of soil surface the comparative compound propanil had practically no efiect on weeds, whereas the two compounds according to the invention surprisingly had a very broad, effect on weeds, i.e. they controlled dicotyledons such as'Sinapis, Ipomoea, Anthemis, Stellaria and Amaranthus as well' as monocotyledons such as Poa, Echinochloa, Eleusine and'Leptochloa. .1 This broad herbicidal effectis of advantage-because in practice the natural weed flora is partially controlled only when preparations of the same type are frequently used. For example, with the application of triazine derivatives, broad leafed (dicotyledonous) weeds" are destroyed while gramineous weeds suchas Echinochloa, Leptochloa, "or Eleusinesurvive and spread, whereas preparations onthe basis of nitroanilines, for example 2, 6 -dinitro-4-trifluoro"- methyl-N,N dipropylaniline "'(trifluralin) "have 'a very goodelfecton gramineous weeds butdopractically no harm to dicotyledons' such as Ipomoea. As compared therewith, the novel compounds according to the invention control the two types of weeds with equally good effect. The reactions of the treated plants already show in thestage of germination, i.e. the plants die "Before they pierce the surface of the soil.

Compound I did but little harm, if any, only to cotton, sunflower, tomato and cabbage, while Compound II did not harm or little harm only to cotton, tomato, cabbage, pea, horse bean, dwarf bean, maize, millet, peanut, tobacco and celery.

EXAMPLE 28 Compounds XVI and XXV were compared with propanil with respect to their etfect in the same manner as described in Example 27. The compounds were applied in the form of an aqueous suspension of wettable powder and the results were evaluated after 4 weeks. The results are indicated in the following Table B;

10 a broad spectrum herbicidal effect was obtained since gramineous weeds, for example Echinochloa, Poa, Eleusine, Leptochloa and Alopecurus, as well as broad leaf weeds such as Arnaranthus, Stellaria and Chenopodium, were attacked and strongly damaged or even fully destroyed. Simultaneously, no damage was observed in the maize. The comparative compound propanil had practically no effect on the weeds.

EXAMPLE 29 TABLE C Efiect against; Cyperua roiundas in the pre-emergence method. Application of the compounds in the form of suspensions of wettable powders as described in Example 27 XVI I Propanil, 1.0 g./m. 1.0 g./m. 0.5 g./m. 1.0 g./m. 0.5 g./m.

EXAMPLE 3O Post-emergence process .A series of Weeds were sown as described in Example 27 and the post were placed in the greenhouse. Two to three weeks after sowing the grown plants were sprayed with aqueous suspensions of wettable powders of Compounds X, XIII, I and III until dripping from the leaves set in. Propanil 'was used as comparative compound in these example, too. The results were evaluated 2 weeks after the treatment and are summarized in the following Table D.

TABLE D Propanil X XIII I III Type of plant 0.06 0.12 0.06 0. 12 0.06 0.12 0.06 0.12 0.06 0.12

Weeds:

Sinapis anaemia 80 100 95 100 100 100 100 100 100 100 I, parpurea 50 90 70 80 '80 95 50 75 75 85 Galium aparim 40 80 30 95 100 75 85 90 Poa 30 80 90 40 80 50 60 60 Anthemis arveneis 10 20 95 100 95 100 100 100 100 100 Viola tricolor 25 30 85 95 80 90 90 100 90 95 Portulaca oleracea 65 90 100 100 100 100 100 Chenopodium album 90 100 80 100 100 100 100 100 Chrysanthemum 40 50 100 100 95 100 90 95 100 100 Average eflect on weeds, percent; 47.8 67.2 79.4 88 9 86.1 96.1 81.7 89.4 88.9 93.3 Crop plants:

Triticum (wheat) 20 30 10 20 0 0 0 20 0 10 Hordeum distichum (barley) 15 20 0 20 0 10 0 15 0 10 Avena satiaa (oat) 15 30 0 10 0 10 0 10 0 15 v Zea mays (maize) 30 Damage 0 5 0 10 Damage Damage Sorghum vulgare'(mlllet 20 Damage 0 15 0 0 Damage Damage Oryza saliva (rice) 0 0 0 l0 0 0 0 15 10 Arachis hypogaea (peanut 10 30 10 10 0 l5 Damage Damage Medicaqoeativa (lucern) Damage 10 15 0 15 Damage Damage Pisum aatz'vum (pea)- Damage 0 0 10 15 Damage Damage Glycine soja (soybean Damage Damage 0 10 Damage Damage .Phaseolus vulgarz's (dw 30 Damage Damage 0 10 Damage Damage Goasypium hirsutum (cotton). Damage 0 10 0 0 Damage Damage Allium cepa (onio Damage Damage 0 l0 Damage Damage (tobacco) 20 Damage Damage 10 15 0 10 Damage Daucus carota (carrot) Damage Damage 0 10 10 20 Damage TABLE B Eflect against weeds and crop plants in the pre-emergence method with Y -0.25-gram of'actlve'ingredient'per square meter of soil surface" The above table reveals-that the tested compounds are It can be seen that the herbicidal effect of the compounds of theinvention was distinctly superior to that of propanil (cf.*the""indicated average values). Quite generally, the novel compounds have the advantage that they are effective or even very effective against Athemis arvensis and Viola tricolor, which remain practically undamaged by propanil.

A similar diiference in favor of the novel compounds exists in the control of Chrysanthemum segetum and Portluaca oleracea against which propanil has no satisfactory effect. With respect to other types of weeds which are difficult to control, such a Galium or Ipomea, mainly effective in the pre-emergence method. In this case, too, 75 Compound XIII has an advantageous effect. Simultaneously, the compounds of the invention do little harm, if any, only to cereals, such as barley, oat, and wheat.

The comparative propanil was not very harmful to the aforesaid cereals either, but the burnings caused therewith were always more distinct than those obtained with the novel compounds vations distinct burnings could be observed on the leaves. Moreover, COIIIPOImd XIII Could be used in a e er Thus, the novel compound had selectivity advantages in number lof crop plants,b nameily lIfl bmaize, rnillet, rice, crops of millet, wheat, barley and beam peanut ucem soy war co In this connection, it should be noted that in the greentobacco and carrot. The other 3 compounds likewise exhibited a selective efiect in several crop plants. In the house test y hefblcldes l cfly damage crop plants applied amounts, the comparative propanil did little harm, when applied in an amount sufiicient for a herbicidal if y y to some P but Its hefblcldal 6566i Wa effect, although the said herbicides may be well used in too low.

ractice in these cro s. This indicates that over-dosa e Hence It follows that the 4 compounds accordmg to fivhich often occurs ractice ma ause dama e Pro d the invention are much more effective than propanil and p y c g that they have a Wider range f application. ucts, however, which do no harm to crop plants in the EXAMPLE 31 greenhouse when applied in the respective amounts are, PO t r en e ocfiss in most cases, safer in their application even under very -eme c r S p unfavorable conditions. Hence, it follows that in some In the manner descnbed precedlng ex ample crops Compound XXV is safer in its application than the pound XXV was compared with propanil in a greater known dinoseb acetate number of crop plants. For comparison there was further used dinoseb acetate (acetic acid ester of 2,4-dinitro-6- sec-butyl phenol) recommended as herbicide in cultiva- EXAMPLE 32 I tions of cereals and leguminosae. P

TABLE E ost-emergence process Efieet against weeds and crop plants in the post-emergence method with 0.25 g. of active ingredient per square meter of soil surface In the manner descrlbed 111 Example y, oat Din0seb 30 and wheat were sown in the field and after germination Type Plant acetate Pmpan XXV and as soon as the plants had developed 3 to 4 leaves the Weeds: 0 O

Anthems mews 100 20 9o crops were treated w th difierent d ses of Comp unds I, BidBnS pil0sa.... 3( igg 1 g XIII, XXV and X, dmoscb acetate and propanil.

95 85 100 The results obtained 3 weeks after the treatment are 32 32 32 summarized in the following Table F. $3 33 33 The results show that the compounds of the invention Viola tricolor 20 60 100 Average herbicidal mm, per exhibit an excellent effect in the field and that they have Crop gg g; 40 a better efiect against some weeds that are difficult to con- Sorghwnivulaare (millet) 25 75' 0 mil than the comparative compounds, above all against Triticum aestivum (wheat) 0 Hordhu m distlichumbarlsay) 2g 2g g Polygonum perszcaria, Polygonum avzculare, Veronica h u u n $152 sa ti t lm t zgewfiu 2o 55 20' sp., Matrzcaria chamomilla and Agrostemma gzrhago. Vicia faba (horse bean) 0 0 45 TABLE F Efiect against weeds and crop plants in a post-emergence process in the field 0.5 kgJha. of active ingredient 1.0 kg./ha. of active ingredient Dinoseb- Dinoseb- Type of plant I XIII acetate Propanil XXV X acetate Propanil Weeds:

Sinopis aroensis 100 100 100 95 100 100 100 97. 5 Thlaapl arvense 100 100 100 95 100 100 100 97. 5 Polygonum persz'caria 97.5 97.5 75 75 100 95 95 Polygonum aviculare.. 85 95 32.5 32.5 75 75 65 65 Agrostemma gz'thago 100 100 O 95 95 0 Veronica 8p 100 80 95 95 97.5 85 90 Matrican'a chamomilla 95 95 75 32.5 95 95 85 65 Crogplants: t t

T1 tcum E28 191" Minor depressions at the beginning which re idly disa ear in the rocess o flggz gg ggff ff'f:l l:} growth; no visible damage after 3 weeks. p pp p 12 observed with most of the weeds, but against Viola tricolor the compound of the invention was fully eflective, while the comparative compound had practically no eifect. When dinoseb acetate was applied in a number of culti- It should be noticed that the compound according to the invention had a distinctly better effect against Anthemis, Chrysanthemum and Viola than had propanil and that it did not damage crops of cereals and leguminosae. Compared with dinoseb acetate, a great difference could not be EXAMPLE 33 Post-emergence process Compounds XIX, IX, VI, XX, and VIII were tested with respect to their herbicidal eifect as described in Examples 30 and 31. The following results were obtained.

' 'IA'ILL'LE G Eflect against weeds and crop plant in th p -emergence processwlth 0.25 g. of active ingredient per square "meter-f soil surface t v Dinoseb- Type of plant I acetate Propanll XIX IX VI XX VIII @9681 'E- F .Js

Chenopodium album; 100' 95 100 100 75 80 100 P ".1" 100 100" "90 100 100 95 100 Sinapis arvensis g 100 95 90 100 100 100 100 Stellaria media 100 100 100 100 100 100 100 Mercurialia ammo. 100; 100 I 100 95 L90 90. 100 Viola tricolor 20 '60 100 85 75 85 75 Average herbicidal efl'eet, perce 86.7 91.7 96.7 96.7 90.0 91.7 91.2 Crop plants: I l. 1 =1 Triticum aestizmm (wheat) 40 0 0 Hordeum distichum (barley). 30 0 0 0 Medicago autiva (lucern) 60 0 0 Glycine mm: (soybean)... N 40 0 0 0 The indicated values show that firstly the novel compounds are superior to the comparative compounds in their action against Viola tricolor and, secondly, all of them do less harm to barley and wheat and most of them have better sparing properties with respect to lucern and soybean than the comparative compounds.

EXAMPLE 34 Pre-emergence process TABLE II Effect against weeds and crop plants in the pro-emergence process with 0.25 gram of active ingredient per square meter of soil surface Type of plant XIX Propachlor Weeds:

S arv sis 100 60 Anthemis arvenais 100 75 Stellaria media 100 80 C' album- 100 30 Datum stra'mrmium 100 20 Alopecurus muosuroides 95 70 Crop plants: Triticum aestitrum (wheat) 0 50 It can be seen that the compound of the invention destroyed practically without difference all weeds without doing any harm to the wheat.

EXAMPLE 35 A method which is related to the pre-emergence process is the so-called presowing or preplant incorporation method. In the present case, this method was applied in such a manner that the seeds of crop plants and weeds were placed in pots as usual, the amount of preparation to be used was mixed with a small volume of soil, the seeds still lying open were covered with this soil so that from the beginning of germinationthey could take up the active ingredient from the covering soil. The test was evaluated after 4 weeks as usual. The result is indicated in the following Table I.

TAB LE I Effect against weeds and crop plants in the presowlng incorporation method with 0.5 gram of active ingredient per square meter Type of plant Propanil XXII XXIII The results show that in the soil treatment the chemically related propanil had an insufficient effect while the compounds of the invention were fully effective against the weeds and did not damage the wheat. Additionally, one of the novel Compounds XXIII exhibited a considerable effect in the leaf treatment (post-emergence process cf. Example 30) above all against Sinapis, Stellaria, Chenopodium, Ipomoea, and Amaranthus. The dosage to ensure a sufiicient control of the weeds was 0.12 gram of active ingredient per square meter of surface.

What is claimed is:

1. A halocarboxylic acid anilide of the formula (Hal)m /X| NHOO-C-X:

in which X and X represent fluorine X stands for CHCI, Z is N0 Hal represents identical chloro groups and n is 3- 2. The compound of claim 1 wherein the same is 2- nitro 3,4,5 trichloro-(a,a-difluoro-p,fi-dichloro)-propionanilide.

3. The compound of claim 1 wherein the same is 2,4,6- trichloro 3 nitro-(u,a-difluoro-p, 3-dichloro)-propionanilide.

4. The compound of claim 1 wherein the same is 2- nitro 3,4,6 trichloro-(a,a-difluoro-fLB-dichloropropionanilide.

References Cited UNITED STATES PATENTS 3,407,056 10/ 1968 Schwartz 260562 3,405,176 10/1968 Farah et al 260562 3,426,049 2/1969 Baker 260562 2,904,590 9/ 1959 Oxley et al. 260562 2,949,354 8/1960 Todd 71l18 3,681,376 8/1972 Scherer et al 260562 3,197,503 7/1965 Smith et a1. 260562 FOREIGN PATENTS 1,372,475 8/ 1964 France 260562 28,484 11/1969 Japan 260562 29,476 12/ 1969 Japan 260562 (Other references on following page) 3,794,683 15 16 OTHER REFERENCES Suetkin, Chem. Abst., vol. 60, col. 1621d-e 1964).

Sita, Chem. AbsL, vol. 65, col. 4463c (1966). Forbes et al., J. Chem. Soc., pp. 835-39 (1963). 1 Bishop et al., J. Chem. Soc., pp. 3076400964 7 gff z zg zfg sfigg5 phyfwbgy Bammni et Chem- Abstracts, vol; '68Hiteni-77872W Shomova et a1., Microbiology U.S.S.R., vol. 34, pp. r r 1 617620 (July 19-65). V

Bern et al., Chem. Abst., vol. 48, col. 44 56f-1 (1954). B ffi i et 11, Farmaco, Sci VOL 2 pp 12..

Pettit et al., Chem. Abst, vol. 49, co]. 102 86g-10287b 25 19 7 Prokopvich et al., Farmakol. Toksikol. (Kiev), pp. 80- Nagasawa et 211., Chem. Abst., vol. 52, col. 12310e-f 10 84 (1970),

Fernandez-Bolanos et al., Chem. Abst., vol. 55, col. RR MOATZ, Primary Examiner Fukui et al., Chem. Abst., vol. 54, col. 4430b-4431b" (1960). Y 15' 7 1-105; 118; 26()465D 

